Developing a zero-carbon energy economy is an imperative for long term survival of the human species. A potential Nitrogen Economy based on interconversions of nitrogen and ammonia is proposed, but requires the development of new chemistry to break and form N–N bonds. I will share my research group’s approach to N–N bond formation/cleavage occurring at metal-metal bonded dimer sites. The photoelimination of N2 from Ru2-azide complexes generates highly reactive nitrido species. These nitrido compounds can react with C–H bonds and strong nucleophiles, and undergo nearly barrierless bimolecular coupling to form N2. Ru2-ammonia complexes are stable in the Ru2(II,II) oxidation state, but upon oxidation to Ru2(II,III), they spontaneously eliminate N2 via a redox reaction that returns to the Ru2(II,II) oxidation state. This reactivity forms the basis for catalytic and electrocatalytic ammonia oxidation reactions that operate at a low overpotential. I will share our current mechanistic understanding of the ammonia oxidation reaction.

From azides to nitrides; From ammonia to nitrogen: Making and breaking N–N bonds with metal-metal bonded compounds

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